JPH041288A - Hot-melt adhesive - Google Patents

Abstract

PURPOSE:To improve the adhesiveness, thermal aging resistance, etc., by using a specified random copolymer of a 4-12C alpha-olefin and an aromatic vinyl monomer. CONSTITUTION:50-98mol% 4-12C alpha-olefin (e.g. butene-1) and 50-2mol% aromatic vinyl monomer (e.g. styrene) are copolymerized in an inert hydrocarbon medium under atmospheric pressure to 50kg/cm<2> at 20-200 deg.C in the presence of an olefin polymerization catalyst comprising a solid titanium catalyst component having a specific surface of at least 3m<2>/g, an organoaluminum compound catalyst component, and if necessary, an electron-donating component to give a hot-melt adhesive comprising a random copolymer having a melt viscosity at 200 deg.C of 1,000-100,000cPs and a softening point of 40-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a true melt adhesive comprising a random copolymer of an α-olefin having 4 to 12 carbon atoms and an aromatic vinyl monomer. In more detail, it has advantages such as adhesion and processability, excellent environmental aging resistance such as heat aging resistance, packaging, bookbinding, bag making, woodworking, can manufacturing, construction, sanitary use, etc. The present invention relates to a true melt adhesive comprising a copolymer of an α-olefin having 4 to 12 carbon atoms and an aromatic vinyl monomer, which can be used in various fields.

In recent years, hot melt adhesives have seen a rapid expansion in the fields of use due to their advantages over conventional solvent-based adhesives in terms of high-speed application, safety, work environment, and energy savings. On the other hand, conventional hot melt adhesives are compounds mainly composed of base polymers such as natural rubber and tackifiers such as petroleum resins. It is composed of a base polymer such as a petroleum resin and a tackifier such as a petroleum resin, and has a large number of double bonds, so it has poor heat resistance and is susceptible to oxidation during coating.
In addition to vein coloration, there are problems such as changes in adhesive performance over time after adhesion. Therefore, in order to simplify the process (t) and prevent product variations during compounding, we There is a need for adhesive resins that have both the properties of a pace polymerer and a tackifier.

The present inventors conducted extensive research to obtain adhesive resins with excellent environmental aging resistance such as adhesiveness, processability, and heat aging resistance, and found that they were made from specific a-olefins and aromatic vinyl monomers. The present invention is intended to solve the problems associated with the prior art as described above. The object of the present invention is to provide a true melt adhesive made of an a-olefin/aromatic vinyl random copolymer that has excellent adhesiveness, processability, and environmental aging resistance such as heat aging resistance.

1 Kaoru Sako 1 The hot melt adhesive according to the present invention has (a) a structural unit derived from an a-olefin having 4 to 12 carbon atoms in a range of 50 to 98 mol%, and (b) 20
Niokel melt viscosity at 0°C is in the range of 1000 to 1 ooooo centiboise, (c) softening point is 40 to 150°C, carbon number 4 to 12
It is characterized by consisting of a random copolymer of an a-olefin and an aromatic vinyl monomer.

Hereinafter, the hot melt adhesive according to the present invention will be specifically explained.

The hot melt adhesive according to the present invention is composed of an a-olefin/aromatic vinyl random copolymer which is a copolymer of an a-olefin having 4 to 12 carbon atoms and an aromatic vinyl monomer.

Specifically, as the a-olefin having 4 to 12 carbon atoms,
Butene-L, pentene-k, hexene-1, heptene-1, octene-1, nonene-L, decene-L, undecene-1, dodecene-1, and the like. Among them, butene-L pentene-1 is preferably used. These α-
One type of olefin may be used alone, or two or more types may be used in combination.

Specifically, the aromatic vinyl monomer constituting the a-olefin/aromatic vinyl random copolymer includes styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, 0-ethylstyrene, Alkyl-substituted styrenes such as m-ethylstyrene, p-ethylstyrene, propylenestyrene, butylstyrene, halogen-substituted styrenes such as chlorostyrene and bromostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-vinyl-
Examples include vinylnaphthalenes such as 4-methylnaphthalene.

The aromatic vinyl monomers constituting the α-olefin/aromatic vinyl random copolymer may be used alone or in combination of two or more.

Furthermore, for the a-olefin/aromatic vinyl random copolymer, other copolymerizable monomers such as ethylene, propylene, etc. may be added to the above-mentioned numbers within the range that does not impair the purpose of the present invention. Copolymerization is also possible.

In the a-olefin/aromatic vinyl random copolymer, the structural unit derived from the a-olefin having 4 to 12 carbon atoms is in the range of 50 to 98 mol%, preferably 60 to 96 mol%, and the aromatic vinyl The amount of structural units derived from monomers is in the range of 2 to 50 mol%, preferably 4 to 40 mol%.

20 of a-olefin/aromatic vinyl random copolymer
The melt viscosity at 0° C. is in the range of 1000 to 100000 centipoise, preferably 2000 to 5000 centipoise. This characteristic value is a value that serves as a guideline for coatability when using the hot melt adhesive of the present invention.

The softening point (ring and ball method) of the α-olefin/aromatic vinyl random copolymer is 50 to 150°C, preferably 70 to 1
It is in the range of 30°C. This characteristic value is a value that serves as a guideline for the upper limit temperature when using the hot melt adhesive of the present invention.

The a-olefin/aromatic vinyl random copolymer is obtained by copolymerizing an a-olefin and an aromatic vinyl monomer in the presence of an olefin polymerization catalyst.

The olefin polymerization catalyst preferably used in the copolymerization includes a solid titanium catalyst component (a), an organoaluminum compound catalyst component (b), and, if necessary, an electron donor component (
C).

The solid titanium catalyst component (a) contains magnesium, titanium, halogen, and an electron donor as essential components, and the magnesium/titanium (atomic ratio) is greater than 1, preferably 3 to 50, particularly preferably 6-30
and halogen/titanium (W.

The electron donor/titanium (molar ratio) is larger than l, preferably 4 to 100, particularly preferably 6 to 40, and the electron donor/titanium (molar ratio) is preferably 0.1 to 10, particularly preferably 0.2 to 40.
It is 6. Its specific surface area is preferably 3 m27g or more, preferably about 40-1000 m2/g, more preferably about 100-800 m27g. usually,
Simple means such as washing with hexane at room temperature do not remove the titanium compound. And the X@spectrum is
Regardless of the raw material magnesium compound used for the preparation of the catalyst, the magnesium compound exhibits a microcrystalline state or, preferably, a very microcrystalline state compared to the crystallization state of ordinary commercially available magnesium cybaride products. Indicates the condition. It may also contain elements other than the essential components listed in nII, pure gold functional groups, and the like. Furthermore, it may be diluted with an organic or inorganic diluent.

The solid titanium catalyst component (a) is prepared by bringing a magnesium compound, a titanium compound, and, if necessary, an electron donor into contact with each other. Further, in the preparation of the solid titanium catalyst component (a), other reaction reagents, such as compounds such as milk silica, phosphorus, aluminum, etc., may be used depending on the case.

As a method for preparing such a solid titanium catalyst component (a), for example, JP-A-50-108385 and JP-A-50-108385,
Publication No. 0-126590, Publication No. 51-20297,
No. 51-28189 Revolution No. 51-64586 Public Corporation No. 51-92885, No. 51-136625, No. 52-87489, No. 52-10059
Publication No. 6, Publication No. 52-147688, Publication No. 52-10
No. 4593 revolution No. 53-2580 public sail No. 53-4
Publication No. 0093, Publication No. 53-40094, Publication No. 55-
135102 publication, 55-135103 revolution 55-152710 revolution 56-811 public sail 56-11908 revolution 56-18606 revolution 1
Publication F7758-83006, 58-138705
Publication No. 56-18606 No. 58-1387
No. 07 revolution No. 58-138708 public corporation No. 58-1
Publication No. 38709 No. 58-138710 Public Corporation No. 58
It can be produced according to the methods disclosed in various publications such as JP-A-138715, JP-A-60-23404, JP-A-61-21109, JP-A-61-37803, and JP-A-61-37803. The method for producing these solid titanium catalyst components (a) will be briefly described below.

For the preparation of the solid titanium catalyst component (a), a magnesium compound can be used. Examples of the magnesium compound include magnesium compounds having reducing ability and magnesium compounds having no reducing ability.

Here, as a magnesium compound having reducing ability,
For example, formula MgR2-, (in the formula, n is 0≦n<2, R is hydrogen or an alkyl group having 1 to 2 degrees of carbon atoms, an aryl group, or a cycloalkyl group, and when n is O, the two R are Mention may be made of organomagnesium compounds represented by (which may be the same or different, or which are halogen).

Specifically, organic magnesium compounds having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride. ,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds can be used alone or may form a complex with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, impropoxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride.

Ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Alkoxymagnesiums such as 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate; and the like.

These magnesium compounds without reducing ability may be compounds derived from the above-mentioned magnesium compounds having reducing ability or compounds derived during preparation of the catalyst component. In order to derive a magnesium compound that does not have reducing ability from a magnesium compound that has reducing ability, for example, a magnesium compound that has reducing ability is mixed with a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

In addition, magnesium compounds include the above-mentioned magnesium compounds with reducing ability and magnesium compounds without reducing ability, as well as complex compounds, composite compounds, or mixtures of the above-mentioned magnesium compounds with other metals, or other metal compounds. It's okay. Sarabanmi It may be a mixture of two or more of the above compounds, and may be used in a liquid state or a solid state. When the compound is solid, it can be liquefied using alcohols, carboxylic acid aldehydes, amines, metal acid esters, and the like.

Among these, magnesium compounds without reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

There are various tetravalent titanium compounds used for preparing the solid titanium catalyst component (a), but usually Tx(OR) o
Xa-a (R is a hydrocarbon & X is a halogen atom,
Examples include tetravalent titanium compounds represented by 0≦g≦4). More specifically, hawk TiCl1a, T i B
Tetrahalogenated titanium such as ra, TiI, etc.: Ti(OCH3)CI+3, Ti(OC2Hs)CM,, T1(On-C,H,)(:g,, Ti(OC2Hs)Br3, T1(0 Trihalogenated alkoxytitanium such as -iso-C,Ho)Brt: Dihalogenated dialkoxy such as Ti(OCH3)2C1t2, Ti(OC2Hs)2clh, Ti(On-C*Hs)2cI12, Ti(OC2Hs)2Br2 Titanium: Ti(oCH3)3CR.

Ti(OC2H6)acIl.

Ti(On CaHo>scQ.

Monohalogenated trialkoxytitanium such as Ti(OCHs)aBr; Tx(OCH3)-1Tt(OC2HsL, Ti(On-CaHs)a, Ti(○-1so-CaHs)4, Ti(0- 2-
Examples include tetraalkoxytitanium such as (ethylhexyl)4. Among these, titanium tetrahalides and alkoxytitanium trihalides are particularly preferred, and alkoxytitanium trihalides are particularly preferred. These titanium compounds may be used alone or in combination of two or more.

It may also be used diluted with hydrocarbon or halogenated hydrocarbon.

Further, when preparing the solid titanium catalyst component (a), an electron donor can be used if necessary. Examples of such electron donors include nitrogen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, ammonia, amines, Nitrogen-containing electron donors such as nitriles and incyanates can be used. More specifically, alcohols with 1 to 18 carbon atoms, such as methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol. : C6-20 nophenols that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc. Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone , Ketones with 3 to 15 carbon atoms such as benzoquinone Aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde: Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone,
Organic acid esters having 2 to 18 carbon atoms such as δ-valerolactone, coumarin, phthalide, and ethylene carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, and anisyl chloride: Methyl Ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc. with 2 carbon atoms
~20 ethers.

Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, etc.: methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tributylamine,
Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine Nitriles such as acetonitrile, benzonitrile, trinitrile: po such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having a -c bond; examples include alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane.

Furthermore, as the organic acid ester, polyvalent carboxylic acid esters are mentioned as particularly preferred examples. R'-C-OCOR5 R4-C-OCOR' (wherein, R1 is a substituted or unsubstituted hydrocarbon 5R2,
R5 and Re are hydrogen or a substituted or unsubstituted hydrocarbon group, R2 and R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group, R3 and R4 may be connected to each other, and when the hydrocarbon groups R1 to R6 are substituted, the substituents include heteroatoms such as N, OSS, etc. For example, C-0-CS C0OR, C0OH,
Oh.

Examples include compounds having a skeleton represented by (having groups such as 5OiH, CN CNH2, etc.).

Specifically, such polyhydric carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl a-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate,
Diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate,
Aliphatic polycarboxylic acid esters such as diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconate, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexanecarboxylic acid Aliphatic polycarboxylic acid esters such as diisobutyl, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, dimethyl phthalate. n-propyl, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineobentyl phthalate, didecyl phthalate, phthalate Aromatic polycarboxylic acid esters such as benzyl butyl acid, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, and dibutyl trimellitate, and esters of aromatic polycarboxylic acids such as 3,4-furandicarboxylic acid. Preferred examples include acid esters.

Other examples of polyvalent carboxylic acid esters include long chain diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Examples include esters of dicarboxylic acids. Among these compounds, it is preferable to use carboxylic esters, and it is particularly preferable to use polyhydric carboxylic esters, especially phthalic esters.

Electron donors preferably contained in the solid titanium catalyst component (a) include organic or inorganic acid esters, alkoxysilane compounds, aryloxysilane compounds, ethers, ketones, tertiary amines, acid halides, and acid anhydrides. Organic acid esters, alkoxysilane compounds, and aryloxysilane compounds are particularly preferred, and among them, aromatic monocarboxylic acids and 1-carbon
Esters with alcohols of ~8, malonic acid, substituted malonic acid, substituted succinic acid, maleic acid, substituted maleic acid, 1.
Particularly preferred are esters of dicarboxylic acids such as 2-cyclohexyldicarboxylic acid and phthalic acid and alcohols having 2 or more carbon atoms.

Further, these electron donors do not necessarily have to be used as starting materials, but can also be generated during the process of preparing the solid titanium catalyst component. Further, the solid titanium catalyst component may be prepared by contacting cholera with the above-mentioned magnesium compound, titanium compound, and, if necessary, an electron donor, a carrier compound, a reaction aid, and the like.

Such carrier compounds include Al1203.5in
2, B201, MgO, Cab, Tio2, ZnO1
Resins such as Z n Q2, SnO2, BaO, ThO, and styrene-divinylbenzene copolymer are used. Among these, A 1120. ．． 5in2 and styrene-divinylbenzene copolymer are preferred.

As reaction aids, organic and inorganic compounds containing silicon, phosphorus, aluminum, etc. can be used.

Solid titanium catalyst component (a) (±) is prepared by contacting a magnesium insulator, a titanium compound, an electron donor if necessary, and a carrier compound if necessary.

Although there are no particular limitations on the method for preparing such solid titanium catalyst component (a), several examples of the method will be briefly described below.

(1) Method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order This reaction involves the reaction of each component with an electron donor and/or an organoaluminum compound or a 710-gen-containing silicon compound. It is also possible to pre-treat with an auxiliary agent.
The electron donor described above is used at least once.

(2) One liquid magnesium compound having reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid magnesium titanium complex. ) The reaction product obtained in (2) Method (4) of further reacting a titanium compound to the reaction product obtained in (1) or (2),
Further Reacting the Electron Donor and the Titanium Compound (5) The solid material obtained by crushing the magnesium compound, the electron donor, and the titanium compound is mixed with a halogen, a halogen compound, and an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, or a complex compound consisting of a magnesium compound and an electron donor, or a magnesium compound and a titanium compound. Further, after pulverization, the material may be pretreated with a reaction aid and then treated with a halogen or the like. Examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

(6) 19 (7) Catalytic reaction products with metal oxides, organomagnesium compounds, and halogen-containing compounds, in which the compounds obtained in (1) to (4) above are treated with 710 gen, halogen compounds, or aromatic hydrocarbons (8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, an alkoxymagnesium, or an aryloxymagnesium with an electron donor and a titanium compound and/or a halogen-containing hydrocarbon. (9) Hydrocarbon bath method containing at least a magnesium compound and alkoxy titanium A method in which a titanium compound, an electron donor, and optionally a halogen-containing compound such as a halogen-containing silicon compound are reacted.

(10) A liquid magnesium compound that does not have reducing ability and an organoaluminum compound are reacted to precipitate a solid magnesium-aluminum complex, and then,
Method of reacting an electron donor and a titanium compound By such a method, solid titanium catalyst component (a)
The amount of magnesium compound, titanium compound, and electron donor added as necessary varies depending on the seed plasma, contact conditions, contact order, etc., but the amount of electron donor per 1 mole of magnesium The compound is preferably used in an amount of 0.01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol. % tag The titanium compound in liquid state is 0.1 mol to 1000 mol, particularly preferably 1 mol to
It is used in an amount of 200 mol.

The temperature at which these compounds are brought into contact is usually -70°C.
-200°C, preferably 10°C - 150°C.

The solid titanium catalyst component (
After the reaction, a) can be purified by washing thoroughly with a liquid inert hydrocarbon. Inert hydrocarbons used for this purpose include n-pentane, isopentane, n-hexane, isohexane, n-hebutane, n-octane, isooctane, n-decane, n-dodecane, and liquid paraffin. aliphatic hydrocarbons.

Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cymene; halogenated hydrocarbons such as chlorobenzene and dichloroethane; and mixtures thereof. can be exemplified.

Olefin polymerization catalyst GL used in producing the σ-olefin/aromatic vinyl random copolymer used in the hot melt adhesive according to the present invention Solid titanium catalyst component (a) as described above and organic aluminum It consists of a compound catalyst component (b).

As the organoaluminum compound catalyst component (b), for example, (1) - Formula Ra, Am (OR2), H, X.

(In the formula, R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is O≦p3, q
is a number such that O≦q3, and m + n +
p + q = 3).

(2) - A complex alkylated product of Group 1 metal and aluminum represented by the formula MIAQR'a (where Ml is Li, Na, or Ni, and R1 is the same as above) can be mentioned.

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

- Formula R1□AQ (ORa), -; (wherein R1 and R2 are the same as above, am is preferably a number of 1.5≦m≦3), - Formula R1, As+ X, -.

(In the formula, R1 is the same as above. X is halogen, m is preferably O<m<3), one formula R1, An R2-.

(In the formula, R1 is the same as above. m is preferably 2≦m<
3), one formula R', A I+ (OR”) I, xq
(In the formula, R1 and R2 are the same as above, X is halogen,
Ohm≦3.0≦n<3.0≦q<3, m+n+q=
Examples include compounds represented by 3).

More specifically, aluminum compounds belonging to (1) include: trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide. : Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition such as R'e, sA R(OR') s, s; diethyl Dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Partially halogenated alkyl aluminum hydrides such as alkyl aluminum cybarides such as, diethyl aluminum hydride, dialkyl aluminum hydride such as dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dihydride, do, probylaluminum dihydride, etc. Other partially hydrogenated alkyl aluminums; Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, ethylaluminum ethoxybromide.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2Hs)2AQ OAQ
(C2H5)2, (C4Hs) 2A 11OA fl
(C4Hs) 2, (C2H8)2AfI NAl
t (C2Hri2, Ru.

Compounds belonging to (2) above include LtAi (C2H6)J, LiA1 (CvH+s
) 4 etc.

Among the above (1) and (2), it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined.

Olefin polymerization catalyst used in the production process of the a-olefin/aromatic vinyl random copolymer constituting the hot melt adhesive according to the present invention The solid titanium catalyst component (a) and the organoaluminum compound catalyst component ( b)
and, if necessary, an electron donor (c). As the electron donor (C), amines, amides,
Ethers, ketones, nitrites, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid monolides, aldehydes, alcoholates, alkoxy(aryloxy)silanes These include organic acids, amides and salts of metals belonging to Groups 1 to 2 of the periodic table. Salts can be formed by the reaction of organic acids and organometallic compounds.

Specific examples of the electron donor (c) include the electron donor used in the preparation of the solid titanium catalyst component (a) described above. Good results have been obtained by combining organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amines, etc. with electron donors (C
). Particularly when the electron donor in the solid titanium catalyst component (a) is a monocarboxylic acid ester, it is preferable to use an alkyl ester of an aromatic carboxylic acid as the electron donor (C).

Further, when the electron donor in the solid titanium catalyst component (a) is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, as mentioned above as a preferable example, IL
Electron donor (C) It is preferable to use an organosilicon compound represented by the following formula.

R, Si (0°R-), -0 (wherein R and R' are hydrocarbon groups, and 0kn<
4) As an organosilicon compound represented by the general formula as above, specifically l&)limethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane Toxisilane,
Screw. -tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-)lyl dimethoxysilane, bis p-)lyl diethoxysilane, bisethyl phenyl dimethoxysilane, dicyclohexyl dimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane Silane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxanecyclopentyltrimethoxy Silane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxy Silas dicyclopentyljethoxysilane.

Tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane are used. .

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltriptoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane , phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, and the like are preferably used.

Two or more of these organosilicon compounds can also be used in combination. Further, examples of the catalyst for polymerization of realolefin used in the copolymerization include a catalyst formed from a metallocene component (d) and an aluminoxane component (e).

The metallocene component (d) is generally used in the formula M\C, where M is zirconium, titanium or hafnium, L is a ligand having a cycloalkagenyl skeleton, and two , alkylene group Substituted alkylene group May be bonded via a silylene group, x, Y
is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen).

As a ligand having a cycloalkagenyl skeleton, for example, a cyclopentagenyl group, a methylcyclopentagenyl group, an alkyl-substituted cyclopentagenyl group such as a pentamethylcyclopentagenyl group, an indenyl group
Examples include fluorenyl groups.

Examples of alkylene groups include methylene group, ethylene group, propylene group, etc. Substituted alkylene groups include
Examples include isopropylidene groups, and examples of substituted silylene groups include dimethylsilylene groups and diphenylsilylene groups.

x and Y are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. Specifically, examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, an isopropyl group, a butyl group, etc. Examples of the cycloalkyl group include a cyclopentyl pentacyclohexyl group, examples of the aryl group include a phenyl group and tolyl group, and examples of the aralkyl group include a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, ethoxy group, butoxy group, and examples of the aryloxy group include a phenoxy group.

Examples of halogens include fluoride milk, salt fish, bromine, and iodine.

Hereinafter, specific examples of reduction metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be illustrated.

Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)methylzirconium monochloride, Bis(cyclopentagenyl)ethylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium monochloride bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium methoxychloride, bis(silolbentadienyl)zirconium ethoxychloride, ethylenebis(indenyl)dimethyl Zirconium, Ethylenebis(indenyl)zirconium dichloride, Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, Dimethylsilylenebis(cyclopentajenyl)zirconium dichloride, Dimethylsilylenebis(indenyl)zirconium dichloride , dimethylsilylene bis(methylcyclopentagenyl)
Zirconium dichloride.

Further, in the above zirconium compounds, a compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

Aluminoxane component (e) IL can be produced, for example, by the following method.

(1) Compounds containing adsorbed water or salt serum containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. In a hydrocarbon medium suspension,
1 wash (2) where an organoaluminum compound such as trialkylaluminum is added and reacted and recovered as a hydrocarbon solution. The aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent.

Examples of the organoaluminum compound used in producing the aluminoxane solution include the compounds listed above as the organoaluminum compound catalyst component (b).

Among these, trialkyl aluminum is particularly preferably used.

The organoaluminum compounds described above may be used alone or in combination.

1 yen as a solvent used in aluminoxane solution
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc. Fats such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane Examples include hydrocarbon solvents such as cyclic hydrocarbon fish gasoline, petroleum fractions such as gas oil, and halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated compounds. Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

Examples of inert hydrocarbon media used in the copolymerization of a-olefins and aromatic vinyl monomers include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc. Aliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or mixtures thereof. can be mentioned. Further, a-olefin or aromatic vinyl monomer which is liquid at the polymerization reaction temperature described below can also be used.

The amount of each catalyst component used in the polymerization system is based on the reaction volume 11
Component (a) is approximately 0.0 in terms of titanium atoms per 1
001 to about 1.0 mmol, component (b) is mixed so that the amount of metal atoms in component (b) is about 1 to about 500 moles per 1 mole of titanium atoms in component (a), and (C) 0.001 per mole of metal atom in component (b)
Preferably, the amount is from about 10 mol, preferably from about 0.01 to about 2 mol, particularly preferably from about 0.05 to about 1 mol.

The polymerization temperature can be selected as appropriate, preferably from about 20 to about 20
The temperature is preferably about 50 DEG to about 180 DEG C., and the pressure can be selected as appropriate; it is preferably carried out under pressurized conditions of atmospheric pressure to about 50 kg/a12. Polymerization can be carried out in any of the following methods: batchwise, semi-continuously or continuously.

The most effective way to control the molecular weight is to add hydrogen to the car polymerization system, which can be controlled to some extent by changing polymerization conditions such as polymerization temperature and proportions of catalyst components used.

Various additives can be added to the adhesive according to the present invention as required. Examples include softening waxes such as dioctyl phthalate and dibutyl phthalate, petroleum-based polyolefin waxes containing paraffin hooks, wax waxes such as microwax, phenolic or bisphenol-based organic compounds, and antioxidants such as metal soaps.

Further, in the present invention, in addition to the lj a-olefin/aromatic vinyl random copolymer, other base polymers and tackifiers may be used in combination within a range that does not essentially impede the effects of the present invention.

The method for preparing the hot melt adhesive according to the present invention is to prepare a homogeneous melt by stirring a mixture of the various additives described above while heating and melting the mixture as necessary. It is formed into a rod shape while cooling.

This hot melt adhesive is melted again and used for adhesive purposes. For example, it is used for corner gluing of molded products by filling a welding gun with a rod-shaped adhesive.

The hot melt adhesive of the present invention has excellent adhesion and processability, and has excellent environmental aging resistance such as heat aging resistance.For packaging, bookbinding, woodworking, can manufacturing, and construction. It can be used in various fields such as , sanitary, etc.

[Examples] Hereinafter, the present invention will be explained with reference to Examples.
The present invention is not limited to these examples.

As a random copolymer of a-olefin, butene-1
The content is 90.2 mol%, and the viscosity (VS) measured using a Brookfield viscometer at 200°C is 710.
0 centipoise, softening point measured by ring and ball method (R&B
A butente styrene random copolymer with a softening point of 105°C was uniformly melt-coated onto the polyethylene terephthalate surface and allowed to cool naturally.The coating pressure was 56 μm.
A biaxially stretched polypropylene film was placed on top of it and heat-sealed at 120°C and 3 kg/a for 10 seconds to obtain a sample for adhesive strength evaluation. The adhesive strength of the sample was evaluated using the following method [T Mold peeling test M] Peeling speed: 30cl/min [5hear Adhesive Failure T
temperature (SAFT) measurement] Temperature increase rate = 25°C/hour Load: 500g The test results are shown in Table 1.

In Table 1, η is measured using a Brookfield viscometer.
L-, '7g indicates the viscosity measured at 200°C using an Emiller viscosity needle, and R&B softening point indicates the softening point measured by the ring and ball method. Also, PET stands for polyethylene terephthalate, and O
FF indicates a biaxially stretched polypropylene film.

Agricultural Loss @J 2-4 The same operations as in Example 1 were performed except that the α-olefin/aromatic vinyl random copolymer or adhesive base material was changed as shown in Table 1. The results are shown in Table 1.

The same operations as in Example 1 were performed except that polybutene-1 was used instead of the a-olefin/aromatic vinyl random copolymer in Example 1. The results are shown in Table 1.

The same operations as in Example 1 were carried out except that propylene was used instead of butene-1 as the a-olefin in Example 1. The results are shown in Table 1.

Claims (1)

[Claims] (1) (a) The structural unit derived from a-olefin having 4 to 12 carbon atoms is in the range of 50 to 98 mol%, (b) The melt viscosity at 200°C is 1000 to 1000
00 centipoise, and (c) the softening point is from 40 to
150° C. A hot melt adhesive comprising a random copolymer of an a-olefin having 4 to 12 carbon atoms and an aromatic vinyl monomer.